Process for breaking petroleum emulsions



United States Patent PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application November 17, 1952, Serial No. 321,038

32 Claims. (Cl. 252-341) This invention relates to a proceess for breaking petroleum emulsions of the water-in-oil type and is characterized by subjecting such as emulsion to the action of a demulsifier, including certain acidic fractional esters which are disclosed in my co-pending application S. N. 31,033, filed November 17, 1952, and which are derived by esterifying an oxyalkylated amine-modified phenolaldehyde resin condensate with a polycarboxy acid.

Ignoring the preparation of the phenol-aldehyde resin per se the remainder of the reactions fall into three classes: (1) condensation, (2) oxyalkylation, and (3) esterification.

The acidic fractional esters obtained in the manner herein described have utility for various purposes and particularly for the resolution of petroleum emulsions of the water-in-oil type. In this connection it should be noted that the polyhydroxylated reactant or reaction mix ture may be obtained by combining a comparatively large proportion of the alkylene oxide, particularly propylene oxide, or a combination of propylene oxide and ethylene oxide, with a comparatively small proportion of the resin condensate. In some instances the ratio has been as high as fifty-to-one, i. e., the ultimate product of oxyalkylation contained about 2% of resin condensate and approximately 98% alkylene oxide. This was, of course, prior to the esterification step.

Momentarily ignoring the final step of esterification this invention in a more limited aspect, as far as the reactants are concerned which, in turn, are subjected to oxyalkylation and then esterification are, as previously noted, certain amine-modified thermoplastic phenol-aldehyde resins. Subsequent description in regard to the aminemodified resins employed is largely identical with the text as it appears in certain co-pending applications, to wit, Serial No. 288,744, filed May 19, 1952, and Serial No. 301,805, filed July 30, 1952. For purpose of sim: plicity the invention, purely from a standpoint of the resin condensate involved, may be exemplified by an idealized formula as follows:

in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbonatoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equallysatisfactory. The amine residue in the above 2,743,243 Patented Apr. 24, 1956 r6 ICC mediately above is only an over-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to substituted polyalkylene amines of the following structure:

in which R has its prior significance, R" represents a hydrogen atom or radical R, D is a hydrogen atom or an alkyl group, n represents the numerals 1 to 10, and x represents a small whole number varying from 1 to 7 but generally from 1 to 3, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176 dated July 22, 1941, to Blair.

See also U. S. Patent No. 2,362,464 dated November 14, 1944, to Britton et al., which describes alkylene diamines and polymethylene diamines having the formula H H where R represents an alkyl, alkenyl, cycloalkyl, or aralkyl radical, and n represents a comparatively small integer such as 1 to 8.

A further limitation in light of the required basicity is that the secondary amino radical shall not be directly joined to an aryl radical or acyl radical or some other negative radical. Needless to say, what has been stated above in regard to the groups attached to nitrogen is not;

agent such as dimethyl sulfate, benzyl chloride, an alkyl bromide, an ester of a sulfonic acid, etc., so as to yield a compound such as CHI-OH, /H 0\ N'CnHln H CHr-(Jz alkyl The introduction of two such polyamine radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course adds a hydrophile efiect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom.

Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile efiect.

Referring again to the resins as such, it is worth noting that combinations, either resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines particularly monoamines.

Combinations, resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines, particularly monoamines having secondary amino groups. Generally speaking, such materials have fallen into three classes; the first represents non-resinous combinations derived froxn phenols as such; the second class represents resins which are usually insoluble and used for the purpose for which ordinary resins, particularly thermo-setting resins are adapted. The third class represents resins which are soluble as initially prepared but are not heatst'able, i.e., they are heat-convertible, which means they are not particularly suited as raw materials for subsequent chemical reaction which requires temperatures above the boiling point of water or thereabouts.

As to the preparation of the first class, i.e., non-resinous materials obtained from phenols, aldehydes and amines, particularly secondary amines, see United States Patents Nos. 2,218,739 dated October 22, 1940, to Bruson; 2,033,092 dated March 3, 1936, to Bruson; and 2,036,916 dated April 7, 1936, to Bruson.

As to a procedure by which a resin is produced as such involving all three reactants and generally resulting in an insoluble resin, or in any event, a resin which becomes insoluble in presence of added formaldehyde or the like, see United States Patents Nos. 2,341,907, dated February 15, 1944, to Cheetham et al.; 2,122,433, dated July 5, 1938, to Meigs; 2,168,335, dated August 8, 1939, to Heckert; 2,098,869, dated November 9, 1937, to Harmon et al.; and 2,211,960, dated August 20, 1940, to Meigs.

A third class of material which approaches the closest to the herein-described derivatives or resinous amino derivatives is described in U. S. Patent No. 2,013,557, dated February 18, 1936, to Bruson.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho 'or para position, i.e., the pilenols themselves are difunctional phenols. This is a differentiation from the resins described in the aforementioned Bruson Patent No. 2,031,557, insofar that said patent discloses suitable resins obtained from meta-substituted phenols, hydroxybenzene, resorc'inol, p,p'(dihy droxydiph'enyl)-diniethylmethane, and the like, all of which have at least three points of reaction per phenolic nuclei and as a result can yield resins which may be at least incip'i'ently cross-linked even though they are apparently still soluble in oxygenated organic solvents or else are heat-reactive insofar that they may approach insolubility or become insoluble due to the etfect of heat, or added formaldehyde, or both.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunction'al phenols, and depending on the proce du-re employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, 'the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an orth'o posit-ion to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, orany other reactant which tends to form a m'ethylol or substituted methylol group. 7

Apparently there is no similar limitation in re ard to the resins employed in the aforementioned Bruson Fatent 2,031,557, for the reason that one may prepare suit able resins from phenols of the kind already specified which invariably and inevitably would yield a resin having a functionality greater than two in the ultimate resin molecule.

The resins herein employed are soluble in a non-oxygenated hydrocarbon solvent, such as benzene or xylene. As pointed out in the aforementioned Bruson Patent 2,031,557, one of the objectives is to convert the phenolaldehyde resins employed as raw materials in such a way as to render them hydrocarbon soluble, i.e., soluble in benzene. The original resins of U. S. Patent 2,031,557 are selected on the basis of solubility in an oxygenated inert organic solvent, such as alcohol or' dioxane. It is immaterial whether the resins here employed are soluble in dioxane or alcohol, but they must be soluble in benzene.

The resins herein employed as rawv materials must be comparatively low "molal products having on the average- 3 to 6 nuclei per resin molecule. The resins employed in the aforementioned U. S. Patent No. 2,031,557, apparently need not meet any such limitations.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. This apparently is not true of the materials described in aforementioned Bruson Patent 2,031,557 and apparently one of the objectives with which the invention is concerned, is to obtain a heat-convertible condensation product. The condensation product obtained according to the present invention is heat-stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkyla'tion, particularly oxyethylation or oxyprop'ylation, under conventional conditions, i.e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. Without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to to C. if one were using resins of the kind described in U. S. Patent No. 2,031,557 it appears desirable and perhaps absolutely necessary that the temperature be kept relativcly low, for instance, between 20 C. 'andflOO" C., and more specifically at a temperature of 80 to 90 C. There is no such limitation in the condensation roc'edure herein described for' reasons which are obvious in light of what has been said previously.

What is said above deserves further amplification at this point for the reason that itmay shorten what is said subsequently in regard to the production of the herein described condensation products. As pointed out in the instant invention-the resin selected is xylene or benzene soluble, which difierentiates the resins from those employed in the aforementioned Bruson Patent No. 2,031,557. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution, and the resin solution, on the assumption that generally the amine will dissolve in-onc phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 (3., yet the reaction does not go "to completion except by the use "of the higher temperatures. The use of higher temperatures means, of course. that the"condensation.v product obtained at the end of the reaction must not He heat-reactive.- Of course, one 'can'addan oxygenated solvent such' as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensation it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e.,' somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference-to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 32% solution. However, all three reactants can be added in any order. I aminclined to believe that in the presence ofabasic catalyst, such as the amine employed, that theformaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would beimmaterial, of course, if the'formaldehyde reacted with the amine was to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed whichreacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place inwhich three different molecules are simultaneously 3 involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims. Again it is to be emphasized one secondary amino group'as, for example, in the case of tetraethylene pentamine. Such group may or may not be susceptible to oxyalkylation under the conditions described, for reasons which are obscure. Briefly stated, oxyalkylation seems to proceed readily at terminal secondary amino groups but less rapidly and sometimes hardly at all when the same group appears in the center of a large molecule. In the instant situation there are phenolic hydroxyls available which are readily susceptible to oxyalkylation. Assume for the moment that the non-hydroxylated amine contains a plurality of secondary amino groups and that one or more may be susceptible to oxyalkylation. If so, the condensate can be depicted more satisfactorily in the following manner by first referring to the resin condensate and then to the oxyalkylated derivative:

in which the characters have their previous significance, and n is the integer 0 or a small whole number, with the proviso that in each terminal amino radical there must be at least one labile hydrogen atom attached to a nitrogen atom as part of a secondary amine residue.

Thus, one can show it is at least theoretically possible and to some extent probable that oxyethylation does take place in reactions of the kind hereln described, not

only at the phenolic hydroxyl but also at one or more of the available secondary amino groups when they appear. This can be depicted in the following manner:

that at the end of the oxyalkylationstep an esterification step follows.

Since the amines herein employed are nonhydroxylated it is obvious the amine-modified resin is at least-susceptible to oxyalkylation by virtue of the phenolic hydroxyl radicals. Referring to the idealized formula which appeared previously it is obvious the oxyalkylated derivatives, or at least a substantial portion of them, could be indicated in the followingmanner:

in which R"O is the radical of alkylene oxide, such as the ethoxy, propoxy or similar radicals derived from glycide, ethylene oxide, propylene oxide, or the like, and n is a number varying from 1 to 60, with the proviso that one need not oxyalkylate all the available phenolic hydroxyl radicals. In other words, one need only convert two phenolic hydroxyl radicals per resin molecule. Stated another way, n can be zero as well-as a whole number subject to what has been said immediately preceding, all of which will be considered in greater detail subsequently. I p

Actually, what has been said previously may not be as completely an idealized presentation as is desirable due to another factor which may be involved. The factor is this: Although the polyamine is non-hydroxylated and may have a tertiary amine group which is not'su'sceptible to oxyalkylation, it may-have 'more'than in which for simplicity the formula just shown previously has been limited to the specific instance where there is one oxyalkylation-susceptible secondary amino radical 40 as part of the polyamine residue.

In the above formula R"O is the radical of an alkylene oxide such as the ethoxy, propoxy or similar radicals derived from ethylene oxide, propylene oxide, glycide or the like, and n is a number varying from 1 to 60, with the proviso that one need not oxyalkylate all the available phenolic hydroxyl radicals or all the available amino hydrogen atoms to the extent they are present. In other words, one need convert only two labile hydrogen radicals per condensate. It is immaterial whether the labile hydrogen atoms be attached to oxygen or nitrogen.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil type, I prefer to use those which have sufficient hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the esters of the various condensation products may not necessarily be xylene-soluble although they are xylene-soluble in a large number of instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. ,It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is again made to U. 8. Patent 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent the following test appears: a

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of Water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (watenin-oil type) which is apt to reverse on more vigorous shaking and further dilution with Water. If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio l part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficient soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surface-active characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (subsurface-activity) tests for emulsifying properties or selfdispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the buty'lphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent water-insoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits selfemulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test su'ch portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophileproperties herein referred to are such as those exhibited by incipient selfemulsification or the presence of emulsifying properties and go through the range of homogeneous di'spersibility or admixture with water even in presence of added waterinsoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it ispointodout that an emulsification test may be used to-determinc ranges of surface-activity and that such emulsification tests employ a xylene solution Stated another way, itisreally immaterialwhethc'r a1, xylene solution: produces; a $01 or whether it merely pro" amine-modificd-resin condensates and also the resin itself, which is usedas a raw materials; 1

' Part 2 is concerned with appropriatebasic secondary polyamines freefmm a hydroxyl radical which may be employed in the'prsporation of the herein described amine-modified resins or condensates;

Part 3-fis concerned with the condensation reactions involving the resin, thea minc, and formaldehyde to produce the specific products or compounds;

Part 4 is concerned with'the oxyalkylation of the products described in Part 3, preceding;

Part 5 is concerned with the conversion of the polyhydroxylated compounds or reactionmixtures described in Part 4, preceding,.- into acidic fractional esters by means of polycarboxy acids; and

Part 6 is concerned with the resolution of petroleumemulsions of the wii-ter-in oil type by means of the acidic fractional esters previously described.

'In the subsequent text, Parts 1, 2 and 3 appear in substantially the same form as the text of the aforementioned co-pending application, Serial No. 288,744, filed May 19, 1952, and also in aforementioned co-pending application, Serial No. 301,805 filed July 30, 1952. Part 4 is substantially the same as Part 4 as it appears in the last mentioned co-pending application. The text is so presented for both purpose of convenience and comparison. Similarly, Part 5 is substantially the same as it appears in aforementioned co-pending application,

Serial No. 32l,033, filed November 17, 1952.

PART 1 1 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in idealized form by the formula Where the divalent bridge radical is shown as being de rived from foimaldchyde it may, of course, be derived from any other reactive aldehyde having 8.. carbon atoms or less.

Because a resin. is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent This is particularly truewhere the resins are derived from trifunctional' phenols as previously noted. However,

even when obtained from a difunctional phenol, for in!- stance paraphehyl phenol, 'onemay obtain a resin which ,is not soluble in a-nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethylglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test-on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or-in U, 8. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity;-said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon'atoms and reactive toward said phenol'; said resin being formedin the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

. If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary polyamine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R H 0H OH R I H H l H] H NC- 0- C-N H H H H R R n R The basic polyamine maybe designated thus:

. /R' EN in which the various characters have the same significance initial presentation of this formula, then .one be-- comes involved in addeddifliculties in presenting an over subject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combinewith the resin molecule, or even toa very slight extent,

if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following for- As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

0 H OH 1 O H 1 H! 1 RI!I.

R R n R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary senseor without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer,

i. e., one having just 3'units, .or just 4 units, or just 5 units,

or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional valve for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no rea- 11 son for using other than those. which-are lowest-in price. and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I Ex. Position R derived wt No. R of R fromn of resin molecule 1a..-. Phenyl Y Formaldehyde. 3. 5 992. 5 Tertiary butyl. .....do 3. 5 882. 5 Secondary buty 3. 5 882. 5 Cyclohexyl 3. 5 1, 025. 5 Tertiary amyl 3.5 959.5 Mixed secondary 3. 5 B05. 5

and tertiary 3. 5 805. 5 3. 5 l, 036. 5 3. 5 l, 190. 5 3. 5 l, 267. 5 3. 5 1, 344 5 3. 5 1, 498. 5 3. 5 945. 5 3. 5 l, 022. 5 3, 5 1, 330. 5 3. 5 l, 071. 5 d 3. 5 l, 148. 5 Nonyl d 3. 1, 456. 5 Tertiary buty h d 3.6 1,008.5 2041... Tertiary amylm do ..d0 3. 5 1, 085. 5 2la Non do. d 3. 5 1,393. 5 22a-.. Tertiary butyl. t. 2 996. 6 23a-.- Tertiary amyL... 4. 2 1,083. 4 Non 4. 2 1, 430. 6 4. 8 1, 094. 4 4. 8 1, 189. 6 4. 8 1,570. 4

PART 2 As has been pointed out, the amine hereinemployed as a reactant is a basic secondary polyamine and preferably a strongly basic secondary polyamine free from hydroxyl groups, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamincs having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary groupand the other into a secondary amine group. By way of example the following formulas are included. It will be noted they include some polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom;

CH; CH:

HCaHtNCaHtIN H H H ommclnn cmmtenm HQQN i 4NCtHANCIHIN :HtN(CH:)I

' H H. H 7

Another rocedurefo'r producing suitable polyeminn is a reaction involving first an alkylene imine, such a ethylene imine or propylene imine, followed by analkylating agent of the kind described, forexamPle, dimethyl What has been said previously may be illustrated by:

reactions involving a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine, such -as dibutylamine, dibenzylamine, dicyclohexylamine, or

mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such as dimethylsulfate. In a somewhat similar procedure the secondary amine of the kind justspeci fiecl can be reacted with an alkylene oxide such 'as can ylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final step noted above in order to convert the primary amino group into a secondary amino group. 5

Reactions involving thesa'me" twolclasses of reactants.

previously'describedfi. e1, a secondary amine plus an; imine plus anaikylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylating' agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite h ydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

in which X is a small whole number having a value of l or more, and may he'as much as 10 or 12, n is an integer having a value of 2 to. 4, inclusive; m represents the numeral 1 to 2; and m represents a number 0 to 1, with the proviso that the sum oflm plus m equals 2; and R has its prior significance, particularlyas a hydrocarbon radical.

The preparation of such amines hasbeen described in primary 'aminesuch as methylamine, ethyl-amine, eyclo hexylangine etc to produce a: secondary mine of the kind above described, in which one of thejgroups at tached to nitrogen is typified by R. Such haloalkyl 'ethers Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition it-own), as described in U. 8'. Patent No. 2,375,659dated May 8," 1945, to Jones et a1. Inthe above formula R may bemethyl, ethyl, propyl, amyl,,octyl, etc.

Other suitable secondary amines which-can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No.

2,482,546 dated September 20, 1949, to Kaszuba, pro-- vided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following:

betaphenoxyethylamine, gamma phenoxypropyl amine, beta phenoxy alpha methylethylamine, and beta-phenoxypropylamine.

;-Qther secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by 'In light of'the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as C H; I C H: H Np ropyleneNpropyleneN H H (C H3) :NC 1H4NC gHrNC gHsNC 2H4N(C Hg) 2 H H H In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different thanif the reaction took place at the intermediate secondary.

amino radical as differentiated from the terminal group. Again, referring-to the second formula above, although a terminal amino radical is not involved it isobvious again that one could obtain two different structures forfthe' radicals attached to the nitrogen atom united tothe methylene bridge, depending whether the reaction took place at either one of the two outer secondary amino groups, or

at the central secondary amino group. If there are two I points of reactivity towards formaldehyde as'illustrated' by the above examples it is obvious that'one might get a mixtureinwhich in part the reaction took place at one 'pointiand in part at'another point. Indeed, there are ,We'll-known suitable polyamine reactions where "a large variety of compounds might be obtained due to such This can be illustrated multiplicity of reactive radicals. by the following formula:

Over and above the specific examples which have appeared previously, attention is directed to the fact that added suitable polyamines are shown in subsequent Table It.

PART 3 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. cule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diificult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple.

' L Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of .these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact,

.. usually it is apt to be a solid at distinctly higher tempera- Thus, I

tures, for instance, ordinary room temperature. have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and

perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxy genated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene.

reason that in most cases aqueous formaldehyde is em-: ployed, which maybe the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be. used but it is more difiicult perhaps to add a solid material instead of the liquid solution and, everything else being event, water is present as water of reaction. If the solvent Since the resin mole any is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subject to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the products obtained are almost invariably a dark red in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more' sticky and more tacky than the original resin itself. Depending.

on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance,

a 5% solution of hydrochloric acid, acetic acid, hydroxy-- acetic acid, etc. One also may convert the finished prod not into salts by simply adding a stoichiometric amount of any selected acid and removing-any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperatureof not over 150 C. and employing'vacnum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (5) is the reaction mass to be subjected to furth'er reaction in which the solvent, for instance, an alcohol, 1

either low boiling or high boiling, might interfere as in the case of oxyalkylation'Z; and the third factor is this, (c) is an effort to be madeto purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

I have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no -objection, of course, to giving the reaction an op portunity to proceed as far as it will at some low temperature', for instance, 30 to 40 butultirnatelyone must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical,

in fact, it may be anything from a few hours up to 24 hours. I have not found any 'case where it was necessary to even' desirablyho'ldthe low temperature stage for more than '24 hours. fIn fact, I am notconvineed is any advantage in holding it at this stage for than 3 or 4 hours at the most. This, again, is amajtter lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents andreactants are selected so the reactants and products of reaction are mutually soluble, then agitation is requiredponly to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is notnecessary as previouslyf pointed out but may be convenient under certain circumstances.

. On the other hand, if the products are not mutually solu-' ble then agitation should be more vigorous for the reason; that reaction probably takesplace principally at the inter faces and the more vigorous the agitation the more inter-'- facial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should belong enough to insure that the resin added, preferably in! powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form,

just as preparation is described in aforementioned U.'S."

Patent 2,499,368. After the resin is in completesolution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution.

It so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible thatthe initial reaction mass could be a three-phase system instead of a two-phase system although this could be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided thisinitial low temperature'stage is employed. The formaldehyde is then added in a suitable, form. For reasons pointed out I prefer to use a solution" and whether to use a commercial 37% concentrationis simply a matter of choice. In large scale manufacturing there may be some advantage inusing a 30% solution of formaldehyde but apparently this is not true on a smalllaboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it.

easier to control unreacted formaldehyde loss.

On a large scaleif there is any difficulty with formaldehyde loss control, one can use' a more dilute form of The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactoryfor a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place,

and other mechanical or chemical difiiculties are involved. I have found no advantage in using solid formaldehyde. because evenhere water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory pro}- cedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction with or without stirring, depending on whether. or not it is homogeneous, at 30 or .40 C. for 4 or 5 hours, or at the most, up .to 10-24 hours, I then complete thereaction by raising the temperature up to; C., or tlrereabntiuts as required.- The inital low temperature procedure be eliminated -or reduced to merely the shortest period of time which avoids .loss of polyamine orformaldehyde';

17 At a higher temperature I use a phase-separating trap and subject the mixture to reflux condensation'until the water of reactionand the water of solution of the formaldehyde is eliminated. I then permit the temperature 882 grams of theresin identified as 2a preceding were powdered and mixed'with a Somewhat lesser weight of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approxito riseto somewhere about 100 C., and generally slightly mately 30 to 35 C. and 176 grams of symmetrical above 100 C., and below 150 C. by eliminating the dimethylethylene diamine added. The mixture was stirred solvent or part of the solvent so the reaction mass stays vigorously and formaldehyde added slowly. In this parwithin this predetermined range. This period of heating ticcular instance the formaldehyde used was a 30% soluand refluxing, after the water is eliminated, is continued tion and 200 grams were employed which were added in until the reaction mass is homogeneous and then for one a little short of 3 hours. The mixture was stirred vigorto three hours longer. The removal of the solvents is ously and kept within a temperature rangeof'30" to conducted in a; conventional manner in the same way as 46 C. for about 19 hours. At the end of this time it was the removal of solvents in resin manufacture as described refluxed, using a phase-separating trap and a small amount in aforementioned U. S. Patent No. 2,499,368. of aqueous distillate withdrawn from time to time. The Needless to say, as far as the ratio of reactants goes I presence of unreacted formaldehyde was noted. Any unhave'invariably.employedapproximately one mole of the reacted formaldehyde seemed to disappear within apresin based on the molecular weight of the resin molecule, proximately two to three hours after refluxing started. 2- moles of the secondary polyamine and 2 moles of form- As soon as the odor of formaldehyde was no longer dealdehyde. In .some instances I have added a trace of tectible the phase-separating trap was set so as to eliminate caustic as an added catalyst but have found no particular all the water of solution and reaction. After the water advantage in this. In other cases I have used a slight was eliminated part of 'the xylene was removed until the excess of formaldehyde and, again, have not found any temperature reached approximately 152 C. or slightly particular advantage in this. In other cases I have used higher. The mass was kept at this higher temperature a slight excess of amine and, again, have not found for three to four hours and reaction stopped. During any particular advantage in so doing. Whenever feasible this time, any additional water which was probably water I have checked the completeness of reaction in the usual of reaction which had formed, was eliminated by means of ways, including the amount of water of reaction, molecuthe trap. The residual xylene was permitted to stay in lar weight, and particularly in some instances have the cogeneric mixture. A small amount of the sample checked whether or not the end-product showed surfacewas heated on a water bath to remove the excess xylene activity, particularly in a dilute acetic acid solution. The and the residual material was dark red in color and had nitrogen content after removal of unreacted polyamine, if the consistency of a sticky fluid or tacky resin. The any is present, is another index. v j overall time for reaction was somewhat less than 30 hours. I g t f a as been Said P y, little m r In other examples, it varied from a little over 30-hours need be said as to the actual procedure employed for the up to 36 hours. The time can be reduced by cutting preparation of the herein described condensation prodthe low temperature period to approximately 3 to 6 hours. ucts. The following example will serve by way of Note that in Table II following there are a large num illustrationz ber of added examples illustrating the same procedure. Example 1b In each case the'initial mixture was stirred and held at a fairly low temperature (30 to C.) for a period The phenol-aldehyde e in i th one th t ha been 40 of several hours. Then refluxing was employed until identified previously as Example 2a. It was obtained the odor of formaldehyde disappeared. After the odor from a paratertiary butyl phenol and formaldehyde. The of formaldehyde disappeared the phase-separating trap resin was prepared using an acid catalyst which was coms empl ye 0 eparate ut all the Water, both the pletely neutralized at the end of the reaction, v The solutlon and condensation. After all the water had been molecular weight of-th e i was 882 5 -Th1's rr separated enough xylene was taken out to have the final sponded to an ve a f' 'b t 3 ,5 phenolic clei, s the product refluxed for several hours somew ere in the range value for n which excludes the 2 'external nuclei, i. e., of 145 to 150 C., 0r thereabollis- Usually the mixture the resin was largely a mixture having 3 nuclei and 4 y1elded a clear solutlon by the time the bulk ofthe water, nuclei, excluding the 2 external nuclei, or '5 and'6 overall or all of the water, had been removed. I nuclei. The resin so obtained in a neutral state had a No e h t polnted out Prevwusly, 1111s procedure light amber color. is illustrated by 24 examples in TableII. v

TABLE I1 Strength of Reaction Max. R in 1 Amt. Solvent used and Reaction Ex. No. 22 grs' Amine used and amount 518 2112133221 temp" c Q ($1 13 gi s tllgt.

Xylene, 600 g 20-23 26 152 2b Xylene, 450g 20-21 24 150 3b. Xylene, 550g 20-22 28 151 Xylene, 400 g 20-28 36 144 Xylene, 450 g. 22-30 25 156 6b. 21-28 32 150 7b.-. 21-23 30 8b.. 20-25 :15 148 90.. 20-27 as .143 10b 20-22 31 14a 11b Xylene, 500 g 21-26 24 146 mu Xylene, 550g 22-25 as 151 13b Xylene, 400 25-38 :12 141) Xylene, 400 g 21-24 30 152 15b. Xylene, 550 g 21-26 27 145 16b 20-23 25 141 1711. 22-21 29 143 18b. 23-25 36 149 191:. 21-26 32 14a 20b. 21-23 30 14s 21b Xylene, 500g 20-26 36 152 220... Xylene, 440g 21-24 :12 150 23b Xylene, 500g 21-28 25 150 240 Xylene,' 350g I 21-22 28 151 .As to the formulas of the-above amines referredto as amine A through amine H, inclusive, we immediately below:

Noam V on. on

Amine B-.-

i H\ /H NCzHsN Ozfit can! Amine H\ a N tEQ V CHI CHI Amine Hg n QaHcN sHAN H CH3 CH8 Amine H: H:

o NCsHgNCl B Amine F-- (MEAD CzH4)4NC HzCHrCH1N Amine G- r on. cm NC1H4NC2H4NCIH4N H H Amine H- our-cg, V I omen, V onto-c ncnnFommn-cn no-0om CHr-C CHzCH;

PART 4 In preparing oxyalkylated derivatives'of PrQducts'of k the: kind which appear as'examples in Part3, thepros cedures employed are substantially the same as those conventionally used in carrying out oxyalkylations, and for this reason the oxyalkylation step-will hesimply illustrated by the following specificexamples:

Example 10 The oxyalkylation-susceptible compound employed is,

the one previously described and designated as Example .1 b. Condensate lb was in turn obtained from symmetrical dimethylethylene diamine and the resin previously identified as Example 2a. Reference to Table I' shows 10.82 pounds of this resin i along with one pound of finely powdered caustic. soda as a catalyst. Adjust ment was made intheautoclave' to operate at a temperature of approximately C. to

13'0" .CQandat a'pressure'of about'lfi to 20' or 25 "pounds; 25 pounds at the most. In some subsequentexamples pressures up to 35 pounds were employed. a r

.The time regulator was set so as toinject the ethylene oxide in approximately,tlireeequarters 'ot an hour and then continue' stirring for 'lS'minutescr longer,'a :total time of one hour. The reaction went readily and, as a matter of fact, the oxide was taken up almost'immediate'ly. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due -in a large -measure vto excellentagitation and also to the compa'rativelyhi'gh concentration of catalyst. The amount of ethylene oxide'introducod was equal in weight :to the initial condensation product, to wit, 10:82 pounds. This represented a molar ratio of 24.6 moles of ethyleneoxide permoleof condensate- The theoretical molecular weight at the end of the reaction pcriod'was21-64. 'A comparatively small sample,

less than SOgramsgWaswithdrSwn merelytor examinetion as far as solubility or -emulsifying power was con cerned and also for the purpose of'makin'g some testson various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular fortnin subsequentT-ables 3 and 4 The size'of-the autoclave employed was 25 gallons. In innumerable comparable-oxyalkylations I have withdrawn a substantial portion at the-end of each step and continuedoxyalkylation on apartial residual sample. This was not the casein this particularseries. examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

. I Exampk 2c This examplesim'ply. illustrates the further oxya1kyla-.- tion of Examplev 1c, preceding. As previously stated, theoxyalkylation-susceptible compound, to wit, Example lb, present at the beginning of the stage was obviously the sam as at the nd qfzth p o s a (E amp e 6)... to wit, 10.82 pounds. The amount of oxide present in the initial step was 10.82- pounds, the amount of catalyst remained the same, to wit, one pound; and the amount of solvent remained the same. The amount of oxide added Was another 10.82 pounds. all addition of oxide in. these various stage being based on the addition of this particular amount. Thus,- at the end of the oxyethylation step the amount of oxide added; was a total of 2.1.64 pounds and the molal ratio of-ethylene, oxide to resin condensate was 49.2; to 1. The theoretical molecular weight was 3246. I r

The maximum temperature during the operation was 125 C. to C. -The maximum pressure was in the range of 15 to 25 pounds. The time period was one and three-quarters hours.

Example 3c 'step was 32.46 -p'ounds.' The molal ratio of oxide to condensate was 73.8 to l Conditions as far as temperature and pressure-and time wereconce'rned were all the same as in Examples lcand 2c. 'The time period was somewhat longer than in previousexamples, to wit, 2 hours- 'Ihe oxyethylation was; continued and the amount of oxide added. again was-10.82 pounds.- There was no added. catalyst and no added solvent. 7 The theoretical molecularweight at thelend of the reaction period was 5410/ The molal ratio of oxide to condensate was 98.4

Certain 21 to l. Conditionsas far as temperature and. pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 2 /2 hours. The reaction unquestionably began to slow up somewhat.

Example 50 Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 10.82 pounds, bringing the total oxide introduced to 64.92 pounds. The temperature and pressure during this period were the same as before. There wasno added solvent. The time period was 3 hours.

Example 7 c The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 75.74 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8656. The time required for the oxyethylation was a bit longer than in the previous step, to, wit, 4 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 86.56 pounds. The theoretical molecular weight was 9738. The molal ratio of oxide to resin condensate was 196.8 to one. Conditions as far as temperature and pressure were concerned were the same as in the pre-' vious examples and the time required for oxyethylation was 5 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a ZS-gallon autoclave: was employed, although in some instances the initial "oxyethylation was started in a 15-gallon autoclave and-then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables IH and IV, itwill be noted that compounds throgh 40c were obtained by the use of ethylene oxide, whereas 41c through 800 were obtained by the use of propylene oxide alone. p

Thus, in reference to Table III it is to be noted as follows:

- The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate-is indicated in the second column.

The amount of condensate is shown in the third column. Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 10 through 400, the

amount of oxide present in theoxyalkylation derivative is j shown in column 4, although in the initial step since no oxide is present there is a blank.

22 1 When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 2c, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 41c through c are the counterparts of Examples 1c through 400, except that the oxide employed in propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, l1, and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the c series, for ex ample, 36c, 40c, 54c, and 70c. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 10 through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 360 and 40c, involve the use of ethylene oxide first, and propylene oxide afterward. inversely, those compounds obtained from 540 and 70c obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial 0 series such as 360, 40c, 54c, and 700, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 360, consisted of the reaction product involving 10.82 pounds of the resin condensate, 16.23 pounds of ethylene oxide, 1.0 pound of caustic soda, and 6.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table s ,s.. e km mh r m t m m m .m & n 8 6 V M u m m m m m l r S mt .a a w flb 08 S 0 b8 n m, awm me r m mim n man a a a o 2 h 1 o e m 1 8 b w m & c L c o t P mo n n a 0 en d m m e m o u mm Mm Pm hoe bty c myim km w a o tk vrw h FL 3 m t pnm md swrnmn omaw t fiw a r w m mmmama d S maw mm mmm .8 mw enm t a mn l ll 0- uNi o r e Y o h n i m mtmmamvmm am uwa mmi ame: jmmwm n c ew m n mfl m um om md umdn u honmmm v m an mmm mwm i nacmsnu m nnwma wm mo m. e m v ml a u rm M mm m e Pv. d o m m mn r n m mmm omfi aormb PnemOPct 5 m w L.- .pte c mmwm mm aa am 5. .mcwwm nmm m u bm umwn s w o a ef3mc u d v enh ed t V TI ha lp ml 6 ml e ath V. n f 3.1 as wm m mum a m flfl mn h w ntm m mm .L mn e u md w M w mo o.e w v.7 n .t mm m mu a i fell. tfln 9 I n V. t T 0 e 0 wmmmu mamp eu m f M 6 ,S ,W. d m .u ..o u m .0 u r X w .M S t e ifi S than 0 ma n wmm hm m d m P mmv ne wi Jams m X e n b e a t ,u a a n w 0 m 0 e 1 v 6 0 PS 0 v I: 1 a mvm .lm E.w. l m wed w 1 M e a X a .YS 6 v Od e m .ur t m i w m m maa mTmf w w 6 m m t W9 m t. n h 6 .X 1 mmw m m m m wmw e MQJ EW a o nnm f mmfm mm mm mumw f .r.. a .,.SS., 6 m ne w m m w u m md n we a V PWR e S N am n Pt m v The'data given in regard to the Operating conditions is products can be decolorized by the use of clays, bleaching substantially the same as before and appears in Table VI' chars, etc. As far as use in demulsification is concerned,

The products resulting from these procedures may conor some other industrial uses, there is no justification for tain modest amounts of the sol- 20 the cost of bleaching the product.

,orhavesmallamounts,

vents as indicated by the figures in the tables.

the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of un'combined oxide, if

the alkalinity be eliminated in any one of s; (a)- add an acid equivalent to the (b) convert the catalyst into sodium chloride and the amine radical into a hydrochloride; or (c) use an excess of the polycarboxy reactant even though a e -is wasted. All this is discussed in detail More careful examination of this type of material can be made by methods employing the well known Karl Fischer reagents as described in Aquametry, Smith and Mitchelh ln, Intersc ience Publishers,

TABLE III 6. 666 22.22.22 .2 6 5%55 SBSE WS Ex.No.

"oxyalkylitidfi-susceptlblm TABLE-VI TABLE VI Continued Time,

hrs.

Water Kerosene 5 Kerosene Max.

Time pres., 2 pISJ: hrs.

v-umtacaw zozouunmumwwwm-nmzonwwwi Insoluble.-.

Insoluble; Do i e ible. 5

Insoluble.

- o 0 a Y I the OIlgIQaLI'BSI D condensate contributes .a comparatively.

: be insignificant or comparatively, small; frorn a neutraliza easend .q With ths er ac 2 2911. 130-140 3 Do. 3011 l 130440 5-10 3 Dlspersible.

' 3 Insoluble.

As previously pqintedout, the present; invention is. Cont a d h'a dici e s ob a ne f qmt e tq l ylflt sla derivatives; described inllfart 4, immediately preceding, an p y ;v c d tieu fi zlyr ca x l is d suc s d p w thp ma Reid: 0 n y I diglycolic ac sqb pe s r aic ai s ae ic: .acis! -rnaleic. acid ;or anhydrigi id oranhydride Jstable so they are;not; decomposed d uring estcrificatio ey m ?c t inv as man s 36 rsarhqmato as ten. example, the acids obtained gby-dirnerizationpt unsatu-A at d twa dsg atura d monoearh wt c daa or unsaturated; monocarhoxwacids ;;haying -;18 .carbon;;,

"at msefve ee the l=id,,;in;., h h r t ppended claims obviously 'includes theanhydrjdesor; any-other bb iql s. u st ts- My. :P fereaqe; ho ever, t0...use polycarboxyacids; and particularly dicarbQX-y acids,=-havs nqtp en 8 a b t m -t In I the present i'insta the --polyhydrqxylatedreac;;. a s. hav ast: O',LQI':' Q IG .hyd qxy radicals I deed, assuming the, resin pn'it; has three or more phenolic hydroxyls which always would be true, oxyalkylation nec- V essarily must yield at least three reactivehydrorgyl radicals except in the very early stages or very low limit of oxyalkylation as described in the preceding section. If lx ewq fl .methxl lysidrqrwe se .rtlienurahetflq rhn. droxyl radicals would be l er. Since the phenolic jq iaii sql rmay. have se ets mpheae iq..hxdrqxylsl is further opportunity for; a multiplicity of hydroxyl radicals in the reactant which serves as an alcohol iri the esterifica- I Q -st n; Th p e enceota basi zni se x teme n some added complicatiomglue to its inherent salt-forming character. 'If several basic nitrogen atoms happened to be present in a polyhydroxylated reactant the same would be true-tea -gr eaterdegreet- In any-condensate of tbegeneral tygeher'ein deseribcdgand alsoin thettype 9f con-irde n 'sate described in my four co-pe ding applications,-

'Serial Nos. 321 031, 3215032, 3211,0134;lana'eztos's, .in-j

, a i b y th r u t be t e smw bas c..: ,ttes -z:

It is-my preference alwaysrtoadd enough-of a strong acid, such-as hydrochloricacid; or; sulfuric a id, so as'to' ,be stoichiometrially equival ntqto. the tbasleity otthea alkaline catalyst used inv oxya lltylation. v Also, I prefergf jvto use a slight additionalzexcess and; if need-Abe sufiicient to combine with the nitrogen basicity of the reactant,;

' and-if needed annexcess,ower and= above. this amounts.

At the ;worst, if there is no, excess, sorne pf the poly carboxy acid reactant mayz be wasted-in a neutralizing 'lf W iQIl ra h t an n s te fisi tion t as xtsuchsal may however convert intqanqester. However, it is.,m p ti n =1 i e t t xya la es de iv t ve c all fra t o and: u ebasic yr ay i either in mi d; ne. c n pr p the resters substantially. the .SZJQC WQY; astif one'iwr. *es ter-ifying polyhydroxylried: reactants free 1 from any-- nitrogen atom, particularly any ba itrogen atorn As stated in U. S. Patent No.'2,602,060 datethly" l,

29 1952,-to De Groote, the production of esters, including acidic esters (fractional esters) from polycarboxy acids and glycols or other hydroxylated compounds is well known.- Needless to say, various compounds may be used such as the low molal ester, the anhydride, the acyl chloride, etc. However, for purpose of economy it is customary to use either the acid or the anhydride. A conventional procedure is employed. On a laboratory scale on 'e'can employ a resin pot of the kind described in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, and particularly with one more opening to permit the use of a porous spreader if hydrochloric acid gas is to be used as a catalyst. Such device or absorption spreader consists of minute alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as paratoluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange poly-oxyalkylated compounds, and particularly likely to do so if the esterificatio'n temperature is too high. In the case of polycarboxy acids such as diglycolic acid, which is strongly acidic, there is named to add any catalyst. In, the case of highly oxyalkylated compounds, where nitrogenbasicity can be ignored, or almost ignored, the use of hydrochloric gas has one advantage over paratoluene sulforric acid and that is that the end of the reaction it can be removed by flushing out with nitrogen, whereas there is no reasonably convenient means available of removing the paratoluene sulfonic acid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the gas through at an exceedingly slow rate so as to keep the reaction mass acidic. Only a trace of acid need be present. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material. My preference, however, is to use no catalyst whatsoever and to insure complete dryness of the oxyalkylated amine-modified phenol-aldehyde resin as described in the final procedure just preceding Table VII.

The products obtained in Part 4, preceding, may contain a basic catalyst. Using highly oxyalkylated compounds, asv a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is required to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separated in a phase separating trap. As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterification. If there is any further deposition of sodium chloride during the reflux stage, needless to say, a second filtration may be required.

In any event, the product resulting from this pre-treatment is apt to be neutral or basic and particularly slightly basic. If a little more acid is used it may even be acidic. .My preference, as pointed out previously, is that the product be neutral or slightly acidic. Oddly enough, if all the basicity isdue to a basic nitrogen atom or more than one basic nitrogen atom since the resin condensate must invariably and inevitably have at least two basic nitrogen atoms, I have found that in the stages of modest or heavy oxyalkylation the final product indicates that the basicity has been greatly reduced, possibly due to the :hydroxylation or some other elfect. Compare, for example, the reduced basicity of trilethanolamine with that of ammonia. As previously noted, at the worst if all .the catalyst has been removed or neutralized a little of the polycarboxy reactant may be" lost.

Considering the resin condensates which are subjected "to oxyalkylation, not onlyin the present application but also in the four co-pending applications, Serial Nos.

the situation becomes further complicated by the fact that an amine having one or more basic nitrogen atoms,

321,031, 321,032, 321,034, and 321,035, it is apparent.

or even a cyclic structure, also may'havehydroxyl radicals and possibly secondary nitroge'n'groups susceptible to acylation. Such amino groups are apt to disappear for obvious reasons on oxyalkylation, particularly after the initial step of oxyalkylation. Thus, what is said herein in regard to esterification applies with equal force and effect substantially to all hydroxylated compounds described, not only in this application but also in the four co-pending applications noted immediately above.

In any event, such oxyalkylated derivative described in Part 4 is then diluted further with suificient xylene, decalin, petroleum solvent, or the like, so that one has obtained approximately a 65% solution. To this solution there is added a polycarboxylated reactant, as previously described, such as phthalic anhydride, succinic acid,,'or anhydride, diglycolic acid, etc., in the ratio of one mole of polycarboxy reactant for each available hydroxyl radical. The mixture is refluxed until esten'fication is complete as indicated by elimination of water or drop in carboxyl value. Needless to say, if one produces a halfester from an anhydride such as phthalic anhydride, no water is eliminated. However, if it is obtained from diglycolic acid for example, water is eliminated. All such procedures are conventional and have been so thoroughly described in the literature that further consideration will be limited to a few examples and a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any, can be employed. For example, the oxyalkylation can be conducted in absence of a solvent or the solvent removed after oxypropylation. Such oxyalkylated end-product can then be acidified with just enough concentrated hydrochloric acid to just neutralize the residual basic catalyst. To this product one can then add a small amount of anhydrous sodium sulfate (sulficient in quantity to take up any water that is present) and then subject the mass to centrifugal force so as to eliminate the dehydrated sodium sulfate and probably the sodium chloride formed. The clear, somewhat viscous, straw-colored amber liquid, or reddish amber liquid, so obtained may contain a small amount of sodium sulfate or sodium chloride, but in any event, is perfectly acceptable for esterification in the manner described, subject to what has been said previously in regard to basicity due to the basic nitrogen atoms present.

It is to be pointed out that the products here described are not polyesters in the sense that there is a plurality of both hydroxy reactant radicals and acid radicals; the productis characterized by having only one hydroxy reactant radical.

In some instances, and in fact, in many instances, I have found that in spite of the dehydration methods employed above a mere trace of water still comes through, and that this mere trace of water certainly interferes with the acetyl or hydroxyl value determination, at least when a number of conventional procedures are used and may retard esterification particularly where there is no sulfonic acid or hydrochloric acid present as a catalyst. Therefore, I have preferred to use the following procedure: I have employed about 200 grams of the hydroxylated compound as described in Part 4, preceding; I have added about 200 grams of benzene, and then refluxed this mixture in the glass resin pot using a phaseseparating trap until the benzene carried out all the water present as water of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of to possibly C. When all this water or moisture has been removed, I also withdraw approximately 100 grams or a little less benzene and then add the required amount of a carboxy reactant and also about 50 grams of a high boiling aromatic petroleum solvent. These solvents are sold by various oil refineries, and, as far as solvent effect, act as if they were almost completely aromatic in character. Typical distillation data in the particular type I have employed and found very satisfactory is the following:

,50 1111., 242 C. ml., 244 C. 601111., 248 C. ml., 252 C. ml., 252 C.

2 larly vacuumdistillation, then the high boiling;

petroleum solvent-might wellbe replaced by some more expensive-solvent such as decalin or an alkylated decalili which has a rather definite or close range boiling ioint.v

5 The removal of the solvent, of course, is purely a 25 1711., 220 C. mL, 260 C. ventional procedure and requires no elaboration. L; 1 30 ml., 225 C. m1., 264 C. Merely by way of. 'llustration, the following '35 ml.,.230: C. 1111., 270 C. use a-simple procedure, to wit: the hydroxylated com-- 401111., 234 C. rnl., 280 C. pound is mixed with .an; equal weight of xylene and re 45 2111., 237 C. ml., 307 C. p 10 fiiuied at aboutlSSTto 190 C., or somewhat higher, for After this material is added, refluxing is continued and, aprqxmately 8 h after much bun found of course, is at a high temperature, to wit, about t at Instance the reacnon to 17.0 C. If the carboxy reactant is an anhydridqneed: water If ls separated py t usual trap. W less to say, no water of reaction appears; if the carboxy if -u e, when anhydride 18 used there s htfle orreactant is an acid, water of reaction should appear and 15 no of water- 4 r should be eliminated at the above reaction temperature. If it is not eliminated, I simply separate out'another 5 Example R to 10 cc. of benzene by means of the phase-separating trap Y and thus raise the temperature to or 1902C, or gi g gi was the frevwudy even to 200 C., if need be. My preference is not to go 20 1 ample 6 amount cmP above 5 200 grams. The amount of xylene used was 219.7 grams. The use of such solvent is extremely satisfactory, pro- [he Polycarboxy reactant was dlglycollc aclfi and vided one does not attempt to remove the solvent subseamount was f qucmlpy except by vacuum distillation, and provided them perature was C. The time of esterification was :10 is no objection to a little residue. Actually, when these 5 h amount of Walt" out was 8111mm J materials are used for a purpose such as demulsification The Same Procedure Was followed n a mll'fl erbf other the solvent might just as well be allowed to remain. If examples, all of wh1ch'are included in Table VII,- imthe solvent is to be removed by distillation, and particudiately following.

TABLE v11 E N 1 E N Th A111 d 1 8mm 833% 5 31? w X. 0. O X- 0- QOJILW. y 130 year 8S 6 M acid ester of cmpd. of h. c. val cmpd. Polycarbmy reactant reactant, (xylene) n cation, 'out cc.

of h. c. grs. temp.,

grs. grs 5 Q hrs.

59 6, 492 47.5 200 Dlglycolleacld 22.8 219.7 185 10 5c 6, 492 47. 5 200 Phthalic anhydrlde. 25. 2 225. 2 178 10 5c 5, 492 47. 5 200 Maleic anhydride... 10. 7 216. 7 187 7 55 5, 492 47. 5 200 Aconitic acid 29. 5 228. 5 183 11 6c 7, 574 40. 7 200 Diglycel 1e acid 19. 45 216. 8 9 6c 7, 574 40. 7 200 Phthalic anhydride- 21. 5 p 221. 5 197 8 5c 7. 574 40. 7 200 M51510 anhydride..- 14. 2 214 2 192 7. 6c 7, 574 40. 7 200 Adipic acid 21. 2 218. 6 13 230 9,532 43.7 200 Diglycolic acid 20.8 218.0 180 10.5 230 9,632 43.7 200 Phthalic anhydride. 23.1 223.0 177 13 230 9, 332 43. 7 200 Maleic anhydr 15. 3 215. 3 168 7 230 9, 532 43. 7 200 Succlnic anhydr1de 15.8 215.6 190 12 .245 10, 836 38.9 200 Diglycolic acid. 18:55 215.1 185 12 248 10, 836 38. 9 200 Phthalie anhydrlde- 20. 5 220. 5 179 11. 5 24c 10, 833 38. 9 200 Maleic anhydr 13. 55 213. 5 154 7 24 10, 835 38.9 200 Aconitic acid.. 24.1 221.0 195 10v 31 548 45. 8 200 Diglycolie 85111.- 21. 8 21s. 9 192 10. 5 310 11, 648 45.8 5 200 Phllhfllic anhydrlde. 24.2 224.2 197 13 310 I 11, 548 45.8 200 Maleic anhydr 8-. 15.0 215.0 183 7 31 11,548 45.8 200 Adlpic acid 23.8 220.9 194. 8 320 13,104 40.0 200 Phthalic anhydrido. 21.4 221.4 198 12 320 13,104 40.5 200 M'aleic anhydr' 8. 14.2, 214.2 185 8 320 13,104 40.5 200 Dlglycolic acid... 19.4 216.8 188 14.5 320 13,104 40.5 200 Succinic anhydrldc. 14.5 214.5 184 10 47c 11, 902 25. 9 200 Diglycolic acid..-" 12. 4 210. 7 197 12 475 11,902 25.9 200 Phthalic anhydride. 13.7 213.7 195 12 V 470 11,902 25.9 200 M51515 5111-15 0: e 9.05 209.05 189 8 471: 11,90 25.9 200 11505111080111 16.1, 214.4 190 9 480 12,982 23.8 200 Diglycollc 801110 11. 35 209.8 199 13.5 488 12,982 23.8 200 1 119115110 anhydride 12.5 212.5 195 12 480 12.982 23.8 200 Maleic anhydride.. 8.3 208.3 185 7 480 12,982 23.8 200 Adipic anhydrldc... 12.4 210.9 187 '8' 630 13, 31. 8 200 Diglycolic acid- 15. 2 213. 1 194 14 63c 13, 244 31.8 200 Phthalic anhydride 15. 9 9 215. 9 198 14 630 13,244 31.8 200 Maleic anhydrlde. V 11.15 211.15 185 12 535 13, 244 31.8 200 Succlm'c anhydride. 11.4 211.4 185 11 64c 14, 448 29.2 200 Diglycollc acid 13.9 212.0 197 13.5 640 14,448 29.2 200 Phthalic anhydrido 15.4 215.4 198 12 64c 14, 448 29. 2 200 Maleic anhydridm. 10.2 210.2 190 10 548 14,448 29.2 200 Aconitlc anhydride- 181 216.2 192 11 71c 15,013 38. 2 200 Diglycolic acid.-. 15. 85 213. 7 200 10. 5 710 15,015 23.2 200 Phthalic anhydriden 17.5 217.5 198- 11 710 15,015 33.2 200 -Maletc-auh ydride. 11:6 211.8 187 8 71 15, 01 33. 2 200 Adipic acid-.. 17. 3 215. 2 192 18 720 17,472 30.5 200 14.5 212.5 198 12 72c 17, 472 30. 5 200 15; 05 215. 05 202 12 721' 17, 472 30. 5 200 10; 8 210.6 190 10 720 17,472 30.5 200 10.85 210.85 188 10 571 8,015 38.4 v 200 28.35 215.9 185 ,8 6d 8,015 38.4 200 20.2 220.2 183 9.5 M 8, 015 38. 4 200 13.45 213. 45 174 5 54 8,015 38.4 200 23.8 223.8 180 p 8 2 7d 8, 556 35. 0 200 17.2 214. 9 190 10. 5 2; 31 71! 8,556 35.0 200 19.0 219.0 185 19 I 711 8, 550 35. 0 200 12. 6 212. 6 179 7 8, 555 35.0 200 18.8 210.5 183 "8 81! 9,097 33. 9 200 Diglyc .182 214.0 180 9- 811 9,097 33.9 200 Phthalicanhydti V --,17.9 217.9 17s :8

TABLE VIIContinued Amt. of Max.

Amt. of Time of Theo hyd. Solvent esterifi- Ex. No. of Ex. No. Theo m.w. h polycarb. estenfi- Water yd. val cmpd. Polycarboxy reactant (xylene), cation, acid ester of cmpd h c. of h c gm reagrtsant, gTs. temp" crgsllgn, out, 00.

8d 9, 097 3.3. 9 200 Maleic anhydride 11. 8 211. 8 172 6 8d 9, 097 33. 9 200 Succlnic anhydride-.- 12.1 212.1 173 8 30d 16, 016 33. 3 200 Dlglycolic acid 16. 4 214. 2 178 10 3011 16, 016 33. 3 200 Phthalie anhydride. 18.15 218.15 175 10 3011 16, 016 33. 3 200 Maleic anhydride. 12. 212. 0 169 7 30d 16, 016 33. 3 200 Aconitic acid 2]. 3 219. 1 172 8 31d 16, 744 31. 8 200 Diglycolic acid 15. 2 213. 2 185 31d 16, 7 31. 8 200 Phthalic anhyd 16. 8 216. 8 178 10 31d 16, 744 31. 8 200 Maleic anhydride. 11. 1 211. 1 187 7 31d 16, 744 31. 8 200 Adipic acid 19. 7 217. 7 183 11 3211 18, 000 29. 6 200 Dlglycolic acid 14. l 212. 2 190 9 32d 18, 000 29. 6 200 Phthalic anhydride. 15. 6 215. 6 197 8 32d 18, 000 29. 6 200 Malelc anhydride 10. 3 210. 3 192 7 32d 18, 000 29. 6 200 Succinic anhydride 10. 5 210.7 195 13 PART 6 other chemical demulsrfier. A mixture whlch lllustrates Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing the present process the treating or demulsifying agent is employed in the conventional manner, well known to the art, described for example in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture, with or without the application of heat, and allowing the mixture to stratify.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 6le with 15 parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

The products herein described may be used not .only in diluted form, but also may be used admixed with some such combination is the following:

Oxyalkylated derivative, for example, the product of Example 61c, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 34%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%. I

The above proportions are all weight percent.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24- carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid "reactant to oxyalkyiated reactant being one mole of the former of each'hydroxyl group present in the latter.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin'being derived by reaction between a difunctional-monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; 'said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radica'l, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the further proviso that the ratio of reactants be approximately 1,2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having and average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei resin molecule; said resin being difunctional only in regard to methylol-form- 36 ing reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin beingtformed in the substantial absence of trifunctional phenolsysaid phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyainine having at least one secondary amino group and having not over 32 carbon atoms .in any-radical attached to any amino nitrogen atoms, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyarnine be free from any primary amino radical, any substituted imi'dazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde;.said condensation reaction being conducted at a temperature suflicien'tly high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon 'atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenolaldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant-to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

. 6. A process'for breaking petroleum emulsions of the 38 water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxalkylated condensate being obtained by the process of first condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula having not over 32 carbon atoms in any radical at-- tached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and. any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting, the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be ap-- proximately 1,2 and 2, respectively; with the furtherproviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation. product resulting from the process be heat-stable and oxy-- alkylation-susceptible; followed by an oxyalkylation stepby means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxalkylated reactant being one mole of theformer for each hydroxyl group present in the latter.

7. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydro phile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

8. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric pheiiol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

9. The process of claim 1 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

10. The process of claim 2 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

11. The process of claim 3 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

12. The process of claim 4 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

13. The process of claim 5 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

14. The process of claim 6 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

15. The process of claim 7 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

16. The process of claim 8 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

17. The process of claim 1 with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 2 with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of Water.

19. The process of claim 3 with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of Water.

20. The process of claim 4 with the-proviso that the 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS; AND SYNTHETIC HYDROPHILE PRODUCTS BEING ACIDIC FRACTIONAL ESTERS OBTAINED BY THE MANUFACTURING PROCESS OF ESTERIFYING (A) AN OXYALKYLATED AMINE-MODIFIED PHENOL-ALDEHYDE RESIN CONDENSATE WITH (B) A POLYCARBOXY ACID; SAID OXYALKYLATED CONDENSATE BEING OBTAINED BY THE PROCESS OF FIRST CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS: SAID PHENOL BEING OF THE FORMULA 